Chromium containing azo dyestuffs



United States Patent CHROMIUM CONTAINING AZO DYESTUFFS Werner Kuster and Guido Schetty, Basel, Switzerland,

assignors to J. R. Geigy A. G., Basel, Switzerland, a

Swiss No Drawing. Application July 12, 1954 Serial No. 442,904 Claims priority, application Switzerland July 20, 1953 6 Claims. (Cl. 260-145) The present invention concerns a process for the production of monoazo dyestlfs, containing chromium in complex linkage, which contain no acid water solubilizing groups. In particular it is concerned-with the production of o,o'-dihydroxyazo dyestuffs, containing chromium, of the type (F -l\ I -F )M wherein F and F represent the same or different o,o'-dihydroxyazo dyestuffs of the S-pyrazolone series, M represents a chromium atom and M represents the equivalent of a cation, in particular a monovalent alkali cation. The new red chromium containing dyestuffs are suitable for the fast dyeing of natural and synthetic polypeptide fibres from a neutral to Weakly acid bath, and they give wool dyeings which in particular are fast to light and also rubbing. The invention therefore enables valuable red dyestuffs to be produced which, because of their good drawing power and their high fastness to light, can be combined in any manner desired when dyeing with other dyestuffs of this class to produce fast fashionable shades on wool.

The known monoazo dyestuffs from nitrated o-hydroxyaminobenzene compounds and l-phenyl-B-methyl-S-pyrazolones containing chromium bound in complex linkage and a sulphamide group, -SO NH in the phenyl radical as a substituent which favourably affects the water solubility, generally have an. insufficient drawing power on to wool in a neutral dyebath and as a result, they are often unfavourable when dyeing in combination with other types of this class of dyestuffs. Depending on the composition, their wool dyeings are also often not very fast to light.

It has now been found that very fast to light complex chromium compounds of monoazo dyestuffs which draw well on to wool even from a neutral bath, areobtained if a monoazo dyestuif of the general Formula I and a monoazo dyestult of the general Formula II which contain no acid water solubilising groups such as e. g. sulphonic acid or carboxyl groups, are reacted with agents giving elf chromium in such amounts that there are two dyestulf molecules linked with one chromium atom.

2,826,572 Patented Mar. 11, 1958 In these formulae: R represents an alkyl or cycloalkyl radical with 4-8 carbon atoms, R represents an alkyl radical with l-S carbon atoms or chlorine, X and X represent the CH -NH NHCH or --NHC H OH group, and Y and Y represent H, -CH or Cl.

Dyestuffs of the general Formula I usable according to the present invention are obtained, e. g. from the following diazo components: 4-n-butyl, 4-tert. butyl-, 4-n-amyl 4-tert. amyl-, 4-cyclohexylor 4-octyl-6-nitro- Z-amino-l-hydroxybenzene.

As azo components such 1phenyl-3-methyl-5-pyrazolones can be used with are substituted in the phenyl radical, preferably in the 3- or 4-position by, for example a sulphonic acid amide, methyl amide, ethanol amide group or by a methyl sulphonyl group and which may contain also methyl or chlorine substituents in the 4- or 6-position for example.

Suitable monoazo dyestuffs of the general Formula II which can be used according to the present invention are obtained from the following diazo components: 4 methyl-, 4isopropyl-, 4-n-butyl-, 4-tert. butyl-, 4-n-amylor 4-tert. amyl-6-nitro-2-amino-hydroxybenzene. As coupling components the 3-methyl-5 pyrazolone compounds listed above as suitable for the production of the monoazo dyestulf I can be used.

The new complex chromium compounds correspond to the formula (F CrF )M wherein F and F represent dyestufis of the general Formula I and II and M represents an alkali metal cation. A suflicient Water solubility of the complex chromium compounds however is only attained if a strongly hydrophilic group, e. g. the sulphamide group -SO NH is chosen asthe solubility promoting substituent. Experience shows that this sulphamide group as substituent in the benzene ring of the coupling component'in symmetrical complex chromium compounds of monoazo dyestuffs obtained from the usual diazo components and l-phenyl-3-methyl- S-pyrazolones, too strongly reduces the drawing power onto wool from a neutral bath. It is therefore often of advantage to combine a dyestuff of the Formula I, the metal complex of which has too little water solubility, with an easily water soluble dyestuif of the Formula II, the metal complex of which has not sufficient drawing power from a neutral bath. In this way, sufficiently soluble mixed chromium complex compounds which draw well from a neutral bath are obtained. For example, it is of advantage to combine a dyestufi of the Formula I having an alkyl radical R which contains from 4 to 8 carbon atoms with a dyestulf of the Formula II which as substituent R has a low molecular alkyl radical, preferably the methyl group. A process which is particularly advantageous technically consists in reacting a diazo compound corresponding to the dyestuif I and a diazo compound corresponding to the dyestulf II with the same coupling component to produce a dyestuff mixture and then to treat this with. agents yielding chromium. The following suitable combinations for example can be named: 6-nitro-4-methyl2-amino-l-hydroxybenzene and 6-nitro-4-tert. butylor tert. amyl-2-amino-l-hydroxybenzene diazotised and coupled with 1-(3'- or 4-sulphonic acid amidophenyl)-3-methyl-5-pyrazolone or with 1-(6'- chloroor -methyl-3'-sulphonic acid-amidophenyD-S- methyl-S-pyrazolone or 1-(4'-chloroor -methyl-3'sul phonic acid amidophenyl)-3-methyl5-pyrazolone or with corresponding sulphonic acid methyl amide, or sulphonic acid methylethanolamide compounds.

The invention however, is not limited to such very similar combinations; less similar mixtures of metallisable pyrazolone dyestuifs can produce valuable chromium containing dyestuffs.

The pyrazolone dyestuffs usable according to the present invention are chromed either in aqueous solution or suspension or in the presence of organic solvents or solubility promoters such as lower alcohols, ether alcohols or fatty acid amides. The process is performed at a raised temperature, if desired under pressure. Chiefly the salts or also the hydroxides of chromium can be used as agents yielding chromium. The use of salts of weak acids is advantageous, e. g. of organic carboxylic acid or the reaction is performed with the mineral acid salts of chromium in the presence of agents neutralising the mineral acid such as sodium acetate. If necessary, also the complex chromium salts can be used with advantage, e. g. the alkali salts of chromcsalicylic acid. In any case, a mineral acid reaction of the medium in the final stage of the metallisation is to be avoided. Of the agents yielding chromium, such amounts are used that there is at least one chromium atom to two dyestulf molecules. If necessary the metallised dyestuffs are finally converted by the action of alkalies or alkaline salts such as sodium or potassium carbonate into the alkali salts. In the production of mixed complexes, the amount of dyestufi I and II does not necessarily have to be stoichiometrical.

In lacquer dyestuifs it is advantageous that the cation of the complex dyestuff-chromium compound be either hydrogen or an organic amine, in textile dyestuffs an alkali or the ammonium cation.

The alkali salts of the new complex chromium compounds are obtained as blue-red powders. Sometimes it may be of advantage to mix them with slight amounts of salts having an alkaline reaction such as sodium carbonate or trisodium phosphate and with anion active wetting and dispersing agents such as soap or synthetic washing agents. They then dissolve in hot water with a bluish-red colour and they dye wool from a neutral to weakly acid bath in fast to light red shades. They are distinguished from similar known compounds by their greater affinity to polypeptide fibres in a neutral to weakly acid bath While at the same time having sufficient water solubility.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees centigrade. The relationship of parts by Iveight to parts by volume is as that of kilogrammes to ltres.

EXAMPLE 1 22.4 parts of 6-nitro-4-tert. amyI-Z-amino-l-hydroxybenzene and 4 parts of sodium hydroxide are dissolved in 200 parts of water, 6.9 parts of sodium nitrite in 35 parts of water are added and the whole is added dropwise at a temperature not exceeding 5 to 25 parts by volume of concentrated hydrochloric acid and 100 parts of water. A yellowish-green suspension of the diazo compound is obtained. On completion of the diazotisation, the acidity of the diazo suspension is neutra'lised with sodium bicarbonate until Congo red paper is no longer coloured blue, whereupon a solution of 27.2 parts of l-(4-methyl- 3-sulphamidophenyl)-3-methyl-5-pyrazolone and 7 parts of sodium hydroxide in 200 parts of water is added. The temperature is then raised overnight from 5 to after which the completely formed dyestuif can be filtered ofif :hrect; it is well washed with 5% sodium chloride solu- -1on.

The filter cakes of this dyestufi are then pasted in 1000 parts of water and 10 parts of ammonia and 100 parts of a solution of ammonium disalicylato chromate containing 3% (by volume) of chromium are added and the whole is heated at 95-100 for 6-8 hours. 50 parts of sodium chloride are then added, the almost completely precipitated complex chromium compound is filtered off gt 8(;), washed with 5% sodium chloride solution and rte The chromium containing dyestuif is. a bluish-red powder which dissolves in hot water with a red and in concentarted sulphuric acid with a yellow-brown colour. It dyes wool from a neutral to weakly acid bath in pure bluish-red shades which have very good fastness properties, in particular good fastness to light.

Very similar dyestufis are obtained if in the above example the diazo component is replaced by 21.0 parts of 6-nitro-4-tert. butyl-Z-amino-l-hydroxybenzene or the coupling component is replaced by 25.8 parts of 1-(3- sulphamidophenyl)-3-methyl-5-pyrazolone or 25.8 parts of l-(4'-sulphamidophenyl)-3-methyl-5-pyrozolone or 27.2 parts of 1-(4'-sulphomethylamido-phenyl)-3-methyl- 5-pyrazolone or 30.3 parts of 1-(4-sulfethanolamidophenyl)-3-methyl-5-pyrazolone or 27.2 parts of 1-(2- methyl-5'-sulphamido phenyl)-3-methyl-5-pyrazolone or 30.3 parts of 1-(4-chlor0-3-sulphamido-phenyl)-3-meth yI-S-pyrazolone.

EXAMPLE 2 22.4 parts of 6-nitro-4-tert. amyLZ-amino-l-hydroxybenzene are diazotised as described in Example 1. On completion of the diazotisation, the suspension of the diazonium compound is neutralised with sodium bicarbonate until Congo red paper is no longer coloured blue. A solution of 26 parts of l-(4-methyl-sulphonylphenyl)-3-methyl-5-pyrazolone and 4.1 parts of sodium hydroxide in 200 parts of water is then added and the temperature of the coupling mixture is raised from 3 to 20 within 10 hours, whereupon the dyestufi is filtered oif and washed with 5% sodium chloride solution.

The filter cakes are then pasted in 1000 parts of water with 10 parts of ammonia 25% at 100 parts by volume of a solution of ammonium disalicylato chromate, containing 3% (by volume) of chromium, is added and the whole is heated for 68 hours at -100". 50 parts of sodium chloride are then added, the completely precipitated complex chromium compound is filtered off, washed with 5% sodium chloride solution and dried.

The chromium containing dyestufi is a bluish-red powder which dissolves in water with a red and in concentrated sulphuric acid with a brown-yellow colour. It dyes wool from a neutral to weakly acid bath in bluish-red shades. The dyeings have very good fastness properties, in particular a very good fastness to light.

Very similar dyestufis are obtained if in the above example the diazo component is replaced by 21.0 parts of 6-nitro-4-tert. butyl-2-amino-1-hydroxybenzene or the coupling component is replaced by 26 parts of l-(3'-methylsulphonyl-phenyl)-3-methyl-5-pyrazolone or by 27 parts of 1-(2-methyl-5'-methyl sulphonyl-phenyl)-3-methyl-5- pyrazolone or by 29.5 parts of l-(2-ch loro-5'-methylsulphonyl-phenyl -3 -methyl-5-pyrazolone.

EXAMPLE 3 Chromium containing dyestuifs which contain two different monoazo dyestuffs can be produced as follows:

The filter cakes of the monoazo dyestuffs I and II which can both be produced as described in Example 1 from:

I. 22.4 parts of 6-nitro-4-tert. amyl-Z-amino-l-hydroxybenzene and 27.4 parts of l-(3-sulphamido-4'-methylphenyl)-3-methyl-5-pyrazolone, and

II. 16.8 parts of 6-nitro-4-methyl-2-amino-l-hydroxybenzene and 27.4 parts of 1-(3-sulphamido-4'-methylphenyl)-3-methyl-5-pyrazolone, are pasted in 2000 parts of water and 20 parts of ammonia 25%. 200 parts of a solution of ammonium disalicylato chromate, containing 3% (by volume) of chromium, are added at 80. The whole is stirred for 6-8 hours at 95-100" and then the chromed dyestutf mixture is precipitated by the addition of 250 parts of sodium chloride. It is filtered off, washed with 5% sodium chloride solution and dried.

The chromium containing dyestufi is a bluish-redpowder which dissolves in water with a red, in concentrated sulphuric acid with a yellow-brown colour. The water solubility of the mixed complex is greater than that of asaasm the uniform complex chromium compounds" of the dye stuffs I and II and the fastness to light is considerably better than that of the uniform chromium complex obtained from dyestuif II. The mixed complex dyes wool from a neutralto weakly'acid-hath in bluish-red shades which have very good fastness properties.

EXAMPLE 4' To produce the monoazo dyestuff I, 23.6 parts of 6- nitro-Z-amino-4-cyclohexyl-l-hydroxybenzene and 4 parts of sodium hydroxide are dissolved in 200 parts of water, 6.9 parts of sodium nitrate in 35 parts of water are added and the mixture is added dropwise at a temperature not exceeding to 25 parts by volume of concentrated hydrochloric acid and 100 parts of water. In this way, a yellowish-green suspension-ofthe diazo body-is obtained. On completion of the diazotisation, the acidity of the diazo suspension is neutralised with sodium bicarbonate until congo paper is no longer coloured bluewhereupon a solution of 25.8parts'of'l (3 sulphamidophenyl) 3- methyl-S-pyrazolone and 7 parts of sodium hydroxide in 200 parts of water are added. The temperature is allowed to rise overnight at 20 and then the completely formed The monoazo dyestufi" His produced in the same manner by diazotising 16.8 parts of 6-nitro-2-amino-4-methyll-hydroxybenzene and coupling with 25.8 parts oil-(3'- sulphamidophenyl -3-methyl-5-pyrazolone;

The filter cakes of both dyestuifs are pasted together in 2000 parts of water and 20 parts of ammonia. 200 parts of a solution of ammonium disalicylatochromate, which contains 3% by volume of chromium, are added at The whole is stirred for 6-8 hours at -100 and then the chromed dyestufi mixture-is separated by the addition of 200 parts of sodium chloride. It is filtered oif, washed with 5% sodium chloride solution and dried.

The chromium containing dyestufi is a bluish powder which dissolves in water with a red, in concentrated sulphuric acid with a yellow-brown colour. Compared with the uniform chromium compounds of the dyestuffs I and II, the mixed complex has an increased water solubility and in contrast with the uniform chormium complexafrom dyestufi II it has considerably better fastness to light. The mixed complex dyes wool from a neutral to weakly acid bath in bluish-red shades which have very good fastness propoerties.

Very similar mixed complexes are obtained if, in the a 5% sodium chloride solution.

It is washed well with above example, the dyestuffs I andII are replaced by the 25 dyestuffs shown under I and II in the following table.

Table No. Monoazo dyestufil' Monoazo dyestufl II Metal Wool dyeing 1 47.4 parts of dyestufl from 6-nltro-4-tert. butyl-Z-amlno-l- 48.8 parts dyestufi from 6-11itro-4-tcrt. amyl-Z-amlno-l- Or Blulsh red.

hydroxybenzene 1-(3-sulphamldophenyl)-3-methylhydroxybenzene 1-(3-sulpham1d0phenyl)-3-methy1- fi-pyrazolone. B-pyrazolone. 4

2 do 45.25 partsdyestuff from 6-n1tro-4-ch10ro-2-amino-1r C D hydroxybenzene 1 (3-su1phamid0phenyl)-3-methy1- fi-pyrazolone.

3 do 44.6 tprarts of dyestuft from fi'nltr0-4-methyl-2-amLuo-1- Or D hy oxybenzene 1-(4-methyl-3-sulphamidophenyl)- 3-methyl-5-pyrazol0ne. I

4 do 48.1 (guts of dyestutl from fi-nitro-4-methyl-2amino-l- (J D by oxybenzene 1-(4-methylsu1phonylphenyl)-3- methyl-5-pyrazolone.

5 do 47.4 parts dyestufi from 6-nitr0-4-tert. buty1-2-amlno-lo Do hydroxybenzene 1-(4-sulphamidophenyl)-3-n1ethylfi-pyrazolone.

6 47.3 parts dyestufi from 6-nltro-4-tert. butyl-z-amlno-ldo Or Do.

hydroxybenzene 1-(4-methy1sulphonylphenyl)-3- methyl-5-pyrazolone.

7 do 43.1 parts dyestufi from 6-nitro-4-methyl-2-amino-1- Or Do,

hydroxybenzene 1-(3-methylsulphony1phenyl)-3- methyl-B-pyrazolone.

8. 50.2 parts dyestufi from 6-n1tro-4-tert. amyl-z-amino-ldo Or Do.

hydroxybenzene 1-(4-methyl-3-sulphamldophenyl)- 3-methyl-5-pyrazolone.

9 do 43.2 parts dyestufi from 6-111tro-ei-methylQ-amjno-L or Do,

hydroxybenzene 1-(3-sulphamidophenyl)-3-metl1ylfi-pyrazolone.

10, do 44.6 parts dyestufi from fi-nitro-4-methyl-2-amino-1- Or Do,

hydroxybenzene 1-pheny1-3-mothyl-5-pyrazolone-3- sulphonic acid methylamide.

11.-.. 50 parts dyestutl from fi-nitroA-eyclohexy1-2-amino-l- 44.6 parts dyestufi from 6-nitro-et-methyl-2-am1no-1- Or Do.

hydroxybenzeue l-pheny1-3-methy1-5-pyrazolone-3'- hydroxybenzene 1-(4-methyl-3-sulphamldophenyl)- sulphamide. 3-methyl-5-pyrazolone.

12 do 43.2 parts dyestufi from 6-11itro-4-methyl-2-amino-1- Or Do,

hydroxybenzene l-(4-sulphamldopheny1)-3-methy1- fi-pyrazolone.

13 do 47.3 parts dyestufl from 6-nitro-4-tert. amyl-2-amlno-1- Or D hydroxybenzene 1-(3"sulphemidophenyl)-3-methy1- 5-py'razolone.

14 do 44.6 parts dyestufi from fi-nltro-4-methyl-2-amlno-1-hy- Or Do,

' droxybenzene 1-(3-sulphmethylamldophenyl)-3- methyl-B-pyrazolone.

15 54.4 parts dyestufl from G-nltro-4-cyelohexyl-2-amino-1- 51.8 parts dyestufi trom 6-nitro-4-tert. buty1-2-amino-1- Or Do.

hydroxybenzene 1-phenyLB-methyl-5-pyrazolone-3- hydroxybenzene l-(3-sulphethanolamidophenyl)-3- sulphethanolamlde. methyl-fi-pyrazolone.

16.- 53 parts dyestufi from 6-nitro-4-octyl-2-amino-l-hydroxy- 43.2 parts dyestuft from G-mtrcA-mcthyl-Zamlno-l-hy- Or Do.

'beinizene 1-phenyl-3-methyl-5-pyrazolone-3-sulphadroxyblenzene 1-(3-sulphamidophenyl)-3-methyl-5- m e. pyrazo one. 17 do 51.8 parts dyestufi from fi-nitro--tert. butyl-Z-amino-l- Or D hydroxybenzene 1-(3'-sulphethanolamidophenyl)-3- methyl-5-pyrazolone. I

18 54.4 parts dyestufiirom 6-nitro-4-cctyl-2-amlno-1-hydr0xy- 44.6 parts dyestufl from 6-nltro-4-methyl-2-amino-lvhy- Or D benzene-e4-tolyl-3-methyl-5-pyrazolone-3-sulphamlde. droxybenzene 1-(4'-methy1-3-sulpham1dophenyl)-3- methyl fi-pyrazolone.

19.". 63 parts dyestufl from 6-nltro-4-oetyl-2-amino-1-hydroxy- ....-do or Do.

beinlzene 1-phenyl-3-methyl-5-pyruzolone-4'-sulpha- 20 do 43.1 parts dyestufi from 6-nltro-4-methyl-2-amlno-l-hy- Or Do.

droxybenzene 1 (4' -methylsulphonylphenyl) -3- methyl-fi-pyrazolone.

2L..- 48.8 parts dyestufi from 6-nitro-4-tert. amyl-2-amino-l- 43.2 parts dyestufi from 6-nltro-4-methyl-2-amlno=l- Or Do.

hydroxybenzene 1-(3-sulphamldophenyl)-3-methylhydroxybenzene 1-(3-sulphamidophenyl)-3-methylfi-pyrazolone. 5-pyraz010ne.

22 .do 45.25 parts dyestufi from 6-nitro-4-ch1oro-2-amino-1-hy Or Do.

droxybenzene 1-(3-sulphamidophenyD-3-methyl-5- pyrazolone.

EXAMPLE parts of wool are entered at 40 into a solution of 0.2 part of the chromium containing dyestuff according to example 1 in 400 parts of water containing 0.3 part of ammonium acetate. The bath is brought to the boil within minutes and boiling is continued until it is practically exhausted which is the case after another 30 minutes. The wool which has been dyed a strong bluish-red colour is rinsed and dried.

What we claim is:

1. A complex chromium compound of the general formula:

wherein M is a cation and F is a co-ordinated monoazo dyestufi of the formula:

and F is a co-ordinated monoazo dyestuff of the formula:

wherein R represents a saturated hydrocarbon radical with from 4 to 8 carbon atoms, R represents a member selected from the group consisting of alkyl radicals with 1 to 5 carbon atoms and chlorine, X and X represent a member selected from the group consisting of CH NH NHCH and NHC H OH and Y and Y represent a member selected from the group consisting of H, CH and Cl.

2. A complex chromium compound of the formula wherein M is a cation and F is a co-ordinated monoazo dyestufl? of the formula 3. A complex chromium compound of the formula (F--Cr-F)M wherein M is a cation and F and F are co-ordinated monoazo dyestuifs of the formula 4. A complex chromium compound of the formula (FCr-F')M wherein M is a cation and F and F are co-ordinated 5. A complex chromium compound of the formula (F-Cr-F)M wherein M is a cation and F and F are co-ordinated monoazo dyestufiis of the formula 6; A complex chromium compound of the formula wherein M is a cation and F is a co-ordinated monoazo dyestufi of the formula and F is a co-ordinated monoazo dyestufi of the formula References Cited in the file of this patent UNITED STATES PATENTS FOREIGN PATENTS Belgium Feb. 12, 1953 OTHER REFERENCES Venkataraman, The Chemistry of Synthetic Dyes, v01.

1, page 533 (1952). 

1. A COMPLEX CHROMIUM COMPOUND OF THE GENERAL FORMULA: 